Modulation of Electron Push-Pull by Redox Non-Innocent Additives for Long Cycle Life Zinc Anode.

Application of an aqueous Zn-ion battery is plagued by a water-induced hydrogen evolution reaction (HER), resulting in local pH variations and an unstable electrode-electrolyte interface (EEI) with uncontrolled Zn plating and side reactions. Here, 4-methyl pyridine N-oxide (PNO) is introduced as a redox non-innocent additive that comprises a hydrophilic bipolar N+-O- ion pair as a coordinating ligand for Zn and a hydrophobic ─CH3 group at the para position of the pyridine ring that reduces water activity at the EEI, thereby enhancing stability. The N+-O- moiety of PNO possesses the unique functionality of an efficient push electron donor and pull electron acceptor, thus maintaining the desired pH during charging/discharging. Intriguingly, replacing ─CH3 (electron pushing +I effect) by ─CF3 group (electron pulling ─I effect), however, does not improve the reversibility; instead, it degrades the cell performance. The electrolyte with 2 m ZnSO4 + 15 mm PNO enables symmetric cell Zn plating/stripping for a remarkable > 10 000 h at 0.5 mA cm-2 and exhibits coulombic efficiency (CE) ≈99.61% at 0.8 mA cm-2 in Zn/Cu asymmetric cell. This work showcases the immense interplay of the electron push-pull of the additives on the cycling.

Design and Piezoelectric Energy Harvesting Properties of a Ferroelectric Cyclophosphazene Salt.

Cyclophosphazenes offer a robust and easily modifiable platform for a diverse range of functional systems that have found applications in a wide variety of areas. Herein, for the first time, it reports an organophosphazene-based supramolecular ferroelectric [(PhCH2 NH)6 P3 N3 Me]I, [PMe]I. The compound crystallizes in the polar space group Pc and its thin-film sample exhibits remnant polarization of 5 µC cm-2 . Vector piezoresponse force microscopy (PFM) measurements indicated the presence of multiaxial polarization. Subsequently, flexible composites of [PMe]I are fabricated for piezoelectric energy harvesting applications using thermoplastic polyurethane (TPU) as the matrix. The highest open-circuit voltages of 13.7 V and the maximum power density of 34.60 µW cm-2 are recorded for the poled 20 wt.% [PMe]I/TPU device. To understand the molecular origins of the high performance of [PMe]I-based mechanical energy harvesting devices, piezoelectric charge tensor values are obtained from DFT calculations of the single crystal structure. These indicate that the mechanical stress-induced distortions in the [PMe]I crystals are facilitated by the high flexibility of the layered supramolecular assembly.

Efficient Piezoelectric Energy Harvesting from a Discrete Hybrid Bismuth Bromide Ferroelectric Templated by Phosphonium Cation.

Bismuth containing hybrid molecular ferroelectrics are receiving tremendous attention in recent years owing to their stable and non-toxic composition. However, these perovskite-like structures are primarily limited to ammonium cations. Herein, we report a new phosphonium based discrete perovskite-like hybrid ferroelectric with a formula [Me(Ph)3 P]3 [Bi2 Br9 ] (MTPBB) and its mechanical energy harvesting capability. The Polarization-Electric field (P-E) measurements resulted in a well-defined ferroelectric hysteresis loop with a remnant polarization value of 2.1 µC cm-2 . Piezoresponse force microscopy experiments enabled visualization of the ferroelectric domain structure and evaluation of the piezoelectric strain coefficient (d33 ) for an MTPBB single crystal and thin film sample. Furthermore, flexible devices incorporating MTPBB in polydimethylsiloxane (PDMS) matrix at various concentrations were fabricated and explored for their mechanical energy harvesting properties. The champion device with 20 wt % of MTPBB in PDMS rendered a maximum peak-to-peak open-circuit voltage of 22.9 V and a maximum power density of 7 µW cm-2 at an optimal load of 4 MΩ. Moreover, the potential of MTPBB-based devices in low power electronics was demonstrated by storing the harvested energy in various electrolytic capacitors.

Process-Structure-Formulation Interactions for Enhanced Sodium Ion Battery Development: A Review.

Before the viability of a cell formulation can be assessed for implementation in commercial sodium ion batteries, processes applied in cell production should be validated and optimized. This review summarizes the steps performed in constructing sodium ion (Na-ion) cells at research scale, highlighting parameters and techniques that are likely to impact measured cycling performance. Consistent process-structure-performance links have been established for typical lithium-ion (Li-ion) cells, which can guide hypotheses to test in Na-ion cells. Liquid electrolyte viscosity, sequence of mixing electrode slurries, rate of drying electrodes and cycling characteristics of formation were found critical to the reported capacity of laboratory cells. Based on the observed importance of processing to battery performance outcomes, the current focus on novel materials in Na-ion research should be balanced with deeper investigation into mechanistic changes of cell components during and after production, to better inform future designs of these promising batteries.

Visible Light-Driven Highly Selective CO2 Reduction to CH4 Using Potassium-Doped g-C3N5.

Establishment of an efficient and robust artificial photocatalytic system to convert solar energy into chemical fuels through CO2 conversion is a cherished goal in the fields of clean energy and environmental protection. In this work, we have explored an emergent low-Z nitrogen-rich carbon nitride material g-C3N5 (analogue of g-C3N4) for CO2 conversion under visible light illumination. A significant enhancement of the CH4 production rate was detected for g-C3N5 in comparison to that of g-C3N4. Notably, g-C3N5 also showed a very impressive selectivity of 100% toward CH4 as compared to 21% for g-C3N4. The photocatalytic CO2 conversion was performed without using sacrificial reagents. We found that 1% K doping in g-C3N5 enhanced its performance even further without compromising the selectivity. Moreover, 1% K-doped g-C3N5 also exhibited better photostability than undoped g-C3N5. We have also employed density functional theory calculation-based analyses to understand and elucidate the possible reasons for the better photocatalytic performance of K-doped g-C3N5.

Designing Nanoengineered Photocatalysts for Hydrogen Generation by Water Splitting and Conversion of Carbon Dioxide to Clean Fuels.

Semiconductor photocatalysis has received tremendous attention in the past decade as it has shown great promise in the context of clean energy harvesting for environmental remediation. Sunlight is an inexhaustible source of energy available to us throughout the year, although it is rather dilutely dispersed. Semiconductor based photocatalysis presents one of the best ways to harness this source of energy to carry out chemical reactions of interest that require external energy input. Photocatalytic hydrogen generation by splitting of water, CO2 mitigation, and CO2 conversion to green fuel have therefore become the highly desirable clean and sustainable processes for a better tomorrow. Although numerous efforts have been made and continue to be expended to search and develop new classes of photocatalyst materials in recent years, several significant challenges still remain to be resolved before photocatalysis can reach its commercial potential. Therefore, major attention is required towards improving the efficiencies of the existing photocatalysts by further manipulating them and parallelly employing newer strategies for novel photocatalyst designs. This personal account aims to provide a broad overview of the field primarily invoking examples of our own research contributions in the field, which include photocatalytic hydrogen generation and CO2 reduction to value added chemicals. This account reviews the state-of-the-art research activities and scientific possibilities which a functional material can offer if its properties are put to best use through goal-oriented design by combining with other compatible materials. We have addressed fundamental principles of photocatalysis, different kind of functional photocatalysts, critical issues associated with them and various strategies to overcome the related hurdles. It is our hope that this current personal account will provide a platform for young researchers to address the bottleneck issues in the field of photocatalysis and photocatalysts with a sense of clarity, and to find innovative solutions to resolve them by a prudent choice of materials, synthesis protocols, and approaches to boost the photocatalysis output. We emphasize that a targeted or goal-directed photocatalyst nanoengineering as perhaps the only way to realize an early success in this multiparametric domain.

An Organic-Inorganic Perovskitoid with Zwitterion Cysteamine Linker and its Crystal-Crystal Transformation to Ruddlesden-Popper Phase.

We demonstrate synthesis of a new low-D hybrid perovskitoid (a perovskite-like hybrid halide structure, yellow crystals, P21/n space group) using zwitterion cysteamine (2-aminoethanethiol) linker, and its remarkable molecular diffusion-controlled crystal-to-crystal transformation to Ruddlesden-Popper phase (Red crystals, Pnma space group). Our stable intermediate perovskitoid distinctly differs from all previous reports by way of a unique staggered arrangement of holes in the puckered 2D configuration with a face-sharing connection between the corrugated-1D double chains. The PL intensity for the yellow phase is 5 orders higher as compared to the red phase and the corresponding average lifetime is also fairly long (143 ns). First principles DFT calculations conform very well with the experimental band gap data. We demonstrate applicability of the new perovskitoid yellow phase as an excellent active layer in a self-powered photodetector and for selective detection of Ni2+ via On-Off-On photoluminescence (PL) based on its composite with few-layer black phosphorous.

Temperature Dependence of the Spin Seebeck Effect in a Mixed Valent Manganite.

We report on temperature dependent measurements of the longitudinal spin Seebeck effect (LSSE) in the mixed valent manganite La_{0.7}Ca_{0.3}MnO_{3}. By disentangling the contribution arising due to the anisotropic Nernst effect, we observe that in the low temperature regime, the LSSE exhibits a T^{0.5} dependence, which matches well with that predicted by the magnon-driven spin current model. Across the double exchange driven paramagnetic-ferromagnetic transition, the LSSE exponent is significantly higher than the magnetization one, and also depends on the thickness of the spin-to-charge conversion layer. These observations highlight the importance of individually ascertaining the temperature evolution of different mechanisms-especially the spin mixing conductance-which contribute to the measured spin Seebeck signal.

Understanding the thermal degradation mechanism of perovskite solar cells via dielectric and noise measurements.

Long term stability is a major obstacle to the success of perovskite solar cell (PSC) photovoltaic technology. PSC performance deteriorates significantly in the presence of humidity, oxygen and exposure to UV light and heat. Here the change in charge transport properties of PSC with temperature and the associated significant drop in device performance at high temperature have been investigated. The latter is shown to be primarily due to an increase in charge carrier recombination, which impacts the open-circuit voltage. To understand the pathway of temperature-induced degradation, low-frequency 1/f noise characteristics, and the capacitance-frequency, as well as capacitance-voltage characteristics have been investigated under various conditions. The results show that at high operating temperature accumulation of ions and charge carriers at the interface increase the surface recombination. Aging experiments at different temperatures show high stability of PSCs up to temperature <70 °C, but a drastic, irreversible degradation occurs at higher temperature (≥80 °C). Low-frequency 1/f noise study revealed that the magnitude of normalized noise in degraded perovskite solar cells is four orders of magnitude higher than the pristine device. This study shows the power of low-frequency noise measurement technique as a highly sensitive non-invasive tool to study the degradation mechanism of PSCs.

Anomalous effect of UV light on the humidity dependence of photocurrent in perovskite solar cells.

Effect of oxygen on the humidity dependence of photocurrent in the presence of UV light has been studied for perovskite solar cells. We observed that the magnitude of photocurrent increases with decreasing humidity initially, but below a certain level, the photocurrent starts to decrease when the humidity is reduced by sending dry nitrogen gas. If we decrease the humidity by sending dry air (keeping nitrogen to oxygen ratio same), then this effect is absent. This phenomenon is related to the presence of oxygen in the environment. When humidity is decreased by flowing dry nitrogen, the oxygen present in the environment of perovskite solar cell also reduces. We found that in the reduced oxygen condition, the presence of UV light helps to remove oxygen from the surface of the mesoporous TiO2 which is responsible for the reduction of photocurrent. In the presence of white light, this effect is not observed. To understand the phenomenon we studied low-frequency noise and current-voltage characteristics, and the dielectric properties of perovskite solar cells under various conditions.

Photoluminescence Quenching in Self-Assembled CsPbBr3 Quantum Dots on Few-Layer Black Phosphorus Sheets.

An ordered self-assembly of CsPbBr3 quantum dots (QDs) was generated on the surface of few-layer black phosphorus (FLBP). Strong quenching of the QD fluorescence was observed, and analyzed by time-resolved photoluminescence (TR-PL) studies, DFT calculations, and photoconductivity measurements. Charge transfer by type I band alignment is suggested to be the cause of the observed effects.

Hysteretic DC electrowetting by field-induced nano-structurations on polystyrene films.

Electrowetting (EW) offers executive wetting control of conductive liquids on several polymer surfaces. We report a peculiar electrowetting response for aqueous drops on a polystyrene (PS) dielectric surface in the presence of silicone oil. After the first direct current (DC) voltage cycle, the droplet failed to regain Young's angle, yielding contact angle hysteresis, which is close to a value found in ambient air. We conjecture that the hysteretic EW response appears from in situ surface modification using electric field induced water-ion contact with PS surface inducing nano-structuration by electro-hydrodynamic (EHD) instability. Atomic force microscopy confirms the formation of nano-structuration on the electrowetted surface. The effects of molecular weight, applied electric field, water conductivity and pH on nano-structuration are studied. Finally, the EW based nano-structuration on PS surface is used for the enhanced loading of aqueous dyes on hydrophobic surfaces.

Starch (Tapioca) to carbon dots: an efficient green approach to an on-off-on photoluminescence probe for fluoride ion sensing.

Photoluminescent carbon dots of 4-5 nm size were prepared from starch (Tapioca Sago) through a solution method under mild conditions. The as-prepared carbon dots were used as photoluminescence probes for highly anion selective fluoride ion detection in aqueous solutions. A ready-to-use device is also demonstrated.

Single-layer graphene-assembled 3D porous carbon composites with PVA and Fe3O4 nano-fillers: an interface-mediated superior dielectric and EMI shielding performance.

In this study, a novel composite of Fe3O4 nanofiller-decorated single-layer graphene-assembled porous carbon (SLGAPC) with polyvinyl alcohol (PVA) having flexibility and a density of 0.75 g cm(-3) is explored for its dielectric and electromagnetic interference (EMI) response properties. The composite is prepared by the solution casting method and its constituents are optimized as 15 wt% SLGAPC and 20 wt% Fe3O4 through a novel solvent relaxation nuclear magnetic resonance experiment. The PVA-SLGAPC-Fe3O4 composite shows high dielectric permittivity in the range of 1 Hz-10 MHz, enhanced by a factor of 4 as compared to that of the PVA-SLGAPC composite, with a reduced loss by a factor of 2. The temperature dependent dielectric properties reveal the activation energy behaviour with reference to the glass transition temperature (80 °C) of PVA. The dielectric hysteresis with the temperature cycle reveals a remnant polarization. The enhanced dielectric properties are suggested to be the result of improvement in the localized polarization of the integrated interface system (Maxwell-Wagner-Sillars (MWS) polarization) formed by the uniform adsorption of Fe3O4 on the surface of SLGAPC conjugated with PVA. The EMI shielding property of the composite with a low thickness of 0.3 mm in the X-band (8.2-12.4 GHz) shows a very impressive shielding efficiency of ∼15 dB and a specific shielding effectiveness of 20 dB (g cm(-3))(-1), indicating the promising character of this material for flexible EMI shielding applications.

From waste paper basket to solid state and Li-HEC ultracapacitor electrodes: a value added journey for shredded office paper.

Hydrothermal processing followed by controlled pyrolysis of used white office paper (a globally collectable shredded paper waste) are performed to obtain high surface area carbon with hierarchical pore size distribution. The BET specific surface area of such carbon is 2341 m(2) g(-1). The interconnected macroporous structure along with the concurrent presence of mesopores and micropores makes the material ideal for ultracapacitor application. Such waste paper derived carbon (WPC) shows remarkable performance in all solid-state supercapacitor fabricated with ionic liquid-polymer gel electrolyte. At room temperature, the material exhibits a power density of 19,000 W kg(-1) with an energy capability of 31 Wh kg(-1). The Li-ion electrochemical capacitor constructed using WPC as cathode also shows an excellent energy storage capacity of 61 Wh kg(-1).

Defects in chemically synthesized and thermally processed ZnO nanorods: implications for active layer properties in dye-sensitized solar cells.

We have carried out the effect of post annealing temperatures on the performance of solution-grown ZnO rods as photoanodes in dye-sensitized solar cells. Keeping our basic objective of exploring the effect of native defects on the performance of DSSC, we have synthesized ZnO rods having length in the range of 2-5 µm by a modified sonication-induced precipitation technique. We performed extensive characterization on the samples annealed at various temperatures and confirmed that annealing at 300 °C results in ZnO rods with minimum native defects that have been identified as doubly ionized oxygen vacancies. The electron paramagnetic resonance measurements on the samples, on the other hand, confirmed the presence of shallow donors in the low temperature annealed samples. We also carried out electrochemical impedance measurements to understand the transport properties at different interfaces in the solar cell assembly. We could conclude that solution-processed ZnO rods annealed at 300 °C are better suited for fabricating DSSC with improved efficiency (1.57%), current density (5.11 mA/cm(2)), and fill factor (45.29%). On the basis of our results, we were able to establish a close connection between the defects in the metal oxide electron transporting nano system and the DSSC performance.

Synthesis of an efficient heteroatom-doped carbon electro-catalyst for oxygen reduction reaction by pyrolysis of protein-rich pulse flour cooked with SiO2 nanoparticles.

Development of a highly durable, fuel-tolerant, metal-free electro-catalyst for oxygen reduction reaction (ORR) is essential for robust and cost-effective Anion Exchange Membrane Fuel Cells (AEMFCs). Herein, we report the development of a nitrogen-doped (N-doped) hierarchically porous carbon-based efficient ORR electrocatalyst from protein-rich pulses. The process involves 3D silica nanoparticle templating of the pulse flour(s) followed by their double pyrolysis. The detailed experiments are performed on gram flour (derived from chickpeas) without any in situ/ex situ addition of dopants. The N-doped porous carbon thus generated shows remarkable electrocatalytic activity towards ORR in the alkaline medium. The oxygen reduction on this material follows the desired 4-electron transfer mechanism involving the direct reduction pathway. Additionally, the synthesized carbon catalyst also exhibits good electrochemical stability and fuel tolerance. The results are also obtained and compared with the case of soybean flour having higher nitrogen content to highlight the significance of different parameters in the ORR catalyst performance.

A high performance all-organic flexural piezo-FET and nanogenerator via nanoscale soft-interface strain modulation.

Flexural strain fields are encountered in a wide variety of situations and invite novel device designs for their effective use in sensing, actuating, as well as energy harvesting (nanogenerator) applications. In this work we demonstrate an interesting all-organic device design comprising an electrospun P(VDF-TrFE) fiber-mat built directly on a conducting PANI film, which is also grown on a flexible PET substrate, for flexural piezo-FET and nanogenerator applications. Orders of magnitude stronger modulation of electrical transport in PANI film is realized in this device as compared to the case of a similar device but with a uniform spin-coated P(VDF-TrFE) film. We find that in the flexural mode of operation, the interaction between the laterally modulated nanoscale strain field distributions created by the fibers and the applied coherent strain field strongly influences the carrier transport in PANI. The transport modulation is suggested to occur due to strain-induced conformational changes in P(VDF-TrFE) leading to changes in carrier localization-delocalization. We further show that the fiber-mat based device system also works as an efficient nanogenerator capable of delivering power for low power applications.

Hierarchically nanoperforated graphene as a high performance electrode material for ultracapacitors.

High performance is reported for a symmetric ultracapacitor (UC) cell made up of hierarchically perforated graphene nanosheets (HPGN) as an electrode material with excellent values of energy density (68.43 Wh kg⁻¹) and power density (36.31 kW kg⁻¹). Perforations are incorporated in the graphite oxide (GO) and graphene system at room temperature by using silica nanoparticles as template. The symmetric HPGN-based UC cell exhibits excellent specific capacitance (Cs) of 492 F g⁻¹ at 0.1 A g⁻¹ and 200 F g⁻¹ at 20 A g⁻¹ in 1 M H2SO4 electrolyte. This performance is further highlighted by galvanostatic charge-discharge study at 2 A g⁻¹ over a large number (1000) of cycles exhibiting 93% retention of the initial Cs. These property features are far superior as compared to those of symmetric UC cells made up of only graphene nanosheets (GNs), i.e. graphene sheets without perforations. The latter exhibit Cs of only 158 F g⁻¹ at 0.1 A g⁻¹ and the cells is not stable at high current density.

CdTe-TiO2 nanocomposite: an impeder of bacterial growth and biofilm.

The resurgence of infectious diseases and associated issues related to antibiotic resistance has raised enormous challenges which may possibly be confronted primarily by nanotechnology routes. One key need of critical significance in this context is the development of an agent capable of inhibiting quorum sensing mediated biofilm formation in pathogenic organisms. In this work we examine the possible use of a nanocomposite, CdTe-TiO2, as an impeder of growth and biofilm. In the presence of CdTe-TiO2, scanning electron microscopy (SEM) analysis shows exposed cells without the surrounding matrix. Confocal laser scanning microscopy shows spatially distributed fluorescence, a typical indication of an impeded biofilm, as opposed to the control which shows matrix-covered cells and continuous fluorescence, typical of biofilm formation. Quantitatively, the inhibition of biofilm was ∼57%. CdTe-TiO2 also exhibits good antibacterial properties against Gram positive and Gram negative organisms by virtue of the generation of reactive oxygen species inside the cells, reflected by a ruptured appearance in the SEM analysis.